The appraisal is strongly focussed on challenges associated with the nuclear sector, however these are representative of what is generally encountered by a range of engineering applications. Ensuring structural integrity of key nuclear plant components is essential for both safe and economic operation. Structural integrity assessments require knowledge of the mechanical and physical properties of materials, together with an understanding of mechanisms that can limit the overall operating life. With improved mechanistic understanding comes the ability to develop predictive models of the service life of components. Such models often require parameters which can be provided only by characterisation of processes occurring in situ over a range of scales, with the sub-micrometre-scale being particularly important, but also challenging. This appraisal reviews the techniques currently available to characterise microstructural features at the nanometre to micrometre length-scale that can be used to elucidate mechanisms that lead to the early stages of environmentally-assisted crack formation and subsequent growth. Following an appraisal of the techniques and their application, there is a short discussion and consideration for future opportunities.